Method of producing monofluorophosphates



Patented Sept. 13, 1949 METHOD OF PRODUCING MONOFLUORLO PHOSPHATES Carl 0. Anderson, Tulsa, Okla., assignor to Ozark 'Mahoning Company, Tulsa, Okla., a corporation of Delaware I No Drawing. Application November 28, 1947, Serial No. 788,675 I a: 1..

9 Claims. (0113 50) 1 This invention relates "to the production of monofluorophosphates, particularly the sodium and potassium monofluorophosphates (NazPOsF and K2PO3F), these being salts of monofluorophosphoric acid (HzPOaF) from which they may be prepared by reaction between the acid and sodium and potassium hydroxide (NaOH and KOI-I) respectively. But the sole practical commercial method of producing this acid of which I am aware is by' reaction between hydrogen fluoride (HF) and a suitable compound of phosphorus such as the pentoxide (P205), metaphosphoric acid (HPOs) or the like which is of course attended by all the problems common to reactions in which HF, one of the most reactive chemical agents known, is used as one of the reactants, while the amenability of the H2PO3F to hydrolysis further complicates the manufacture of said monofluorophosphates in this way.

It is therefore an object of the present invention to provide a novel method'of producing an alkali metal monofluorophosphate in which it is not necessary initially to employ HzPOsF, yet one capable of yielding high, almost theoretical quantities of the salt by reaction between stoichiometric proportions of other suitable starting ingredients under controlled conditions.

A further object is to provide a method whereby through reaction between comparatively easily available salts such as the fluoride and corresponding metaphosphate of an alkali metal, a third salt, the monofluorophosphate of the metal may be produced.

Other objects, purposes and advantages of'the invention will hereinafter more fully appear or will be understood from the'following description of what I now consider as the best manner of practising it.

It will be appreciated that as with many chemical processes having to do with fluorine and its compounds care must be taken in the selection of vessels in which the reaction is to be carried out, as some materials of which chemical equipment is made are attacked by fluorine and its compounds although not noticeably affected by many other substances.

Thus in laboratory preparation of the said alkali metal monofiuorophosphates I prefer to use platinum or silver vessels and for production on a commercial scale suitable equipment made of or coated with substances relatively inert to the action of fluorine compounds, although iron equipment is satisfactory where 100% purity ofthe productis not essential.

The monofiuorophosphates of sodium and potassium, which metals as a group will hereinafter be designated generically by the symbol Me, may be produced in accordance with the present method from the fluoride (MeFX'andthe metaphosphate (MePOa) of the respectivemetals although other phosphates may'be used provided they yield the metaphosphateon dehydration by heat Thus the dihydrogen orthophosphates (MG'H2PO4) and/ or the dihydrogen pyrophosphates (MezHzPzov) may be 'used'as sources of the metaphosphates if desired. 1 Furthermore the acid fluorides (MeHFz) may be substituted for the fluorides (MeF) provided that when this substitution is made a suitableagent such as a quantity of the metal carbonate (MezCOs) equivalent to the acid hydrogen of the difluoride be supplied to neutralize the latter as will hereafter more fully appear. f

In practising theinventlon I have found it is only necessary to. bring the metaphosphate (MePOaland the fluoride (MeF) together in a suitable vessel which isinert' or substantially so to the mixture of these salts and to'their reaction product and to close the vessel sufficiently tightly to substantially exolude'moist air during heating to fusion and subsequent cooling of its contents. If complete fusion is not attained during the heating the mass may beonly sintered and the yield of the monofluorophosphate will be less than normal, but there isapparently no advantage to be gained from prolonging the heating once complete fusion of the mass to a homogeneous liquid has been attained, while the rate of cooling is also apparently unimportant, although it is preferred that it be carried out under conditions substantially excluding atmospheric moisture.

While it isconvenient to carry out the invention as a, batch procesaparticularly when small quantities are involved, as inthe laboratory, employment of a continuous pro'cessfor commercial production of the inonofiuorophosphates is envisaged.

When starting materials otherthan the fluoride and the metaphosphateare selected certain preliminary operations" are-"advisable although they can be omltted 'if desired-as their functions may be substantiallyaccomplished incidentally to the main reaction. Thus when'phosphates other than-th metaphosphate are employed they are preferably initially? dehydrated by heating to about 300C; toeliminate the combined, and of course any free-,- waterbefore the phosphate is mixed with thefiuorldei If this is not done there may be excessive hydrolysis losses due to the presence of water in the reacting mass Moreover when the acid fluoride (MBHF2) is employed instead of the fluoride (MeF) and as noted the: corresponding carbonate (MezCOa) used to; neutralize thee acid 'llhydrogeni ofthe former, these two substances are preferably likewise heated together in stoichiometric proportions to release water and carbon dioxide in accordance with the equation:"

the resultant fluoride (MF)"- then-being" com bined with the metaphosphate and heated to fusion as has been described.

Under the preferred conditions using stoichiOj-P metric quantities of either the sodium or the poa, n tassium salts the reaction proceeds substantially able analyticalerror. The absenceiof'free orunwhen removedv from the furnace reactedKF'in the reaction-product 'was confirmed a in acid solution under such conditions that as little as" 1%, free KF. could have been detected;

the.absencerofj'solubl'funreacted KP'OEiIWas'demonstrated. by. the-failure j ofsilven nitrate solution to produce; a; precipitate in a solution obtained from 'the'productlfl l" Example. HA-222363? and 4.6455 g grams K1 05; similarly. 'greu eisna heated for 13 minutes but at 800501011removal;,were found to be sintereditola unitary,v mass but' n'ot entirely melted Analysis at 973% KEPUF. and T-2'.l)% KPO3 jindic atedlthe t'otal-'99T6 %T also contains an analytical error. as evidnc'euof lfi'ee "was observedTinithe reaction. product; Absence of free KE was rurtnemonfirmeeiby disappearance of the turbidity; 'produced'ini solutions. of i the products (by CaCI solution on addition of acid to pH 2. v

Example 'IIL -IQS'IBL gramsa'NaF! and 3.3424 grams: NaPOs mixed and heated in apla-tinum bottle for 9. minutes -in a furnace operating at 660? 0., yielded after. cooling incompletely soluble mass) of substantially, 1 001% vpure magma, "the calcium. nitrateltest showingrentirely negative resuits and thus indicating less'than 1'%;"free-i=1uoride in thewreaction productr Thus it-may be conoludedwthe reaction between Mel. and MeI-loa .lproceeds(substantially to compltion in accordancewith -the.indicated equation to producea monoiiuorophosphate (MezPOaF) that relatively insignificant Weig-ht losses occur; possibly as aresult of some escape (if-constituents in gas or vapor rform landtthat substantial yields of MezPO5F! mayd'bel -readilyr obtained-landtcan be separated from, the-cinsolubles in the reaction s y; solution-1n timeaade e rystailitat o i 4 Solutions of the monofluorophosphates, when treated with solid silver nitrate, produce flat platelets and/or crystals of silver monofluorophosphate (AgzPOaF), the yield of which is substantially increased by adding alcohol to the V filtrate. In one test the total precipitate of AgzPOsF obtained in this manner was 95.6% of theoretical indicatingiathigh degreeio'f purity of the original MGPOaF solutions obtained by dissolving the products of my method in water.

Commercial uses of these monofluorophospirates are :assyet'tnot highly developed, due probably" in large part to the lack heretofore of a practical commercial. method for their production iiix quantitmhbut researches thus far complet edlindicatel they may have wide application in medicine, insecticides, mothproofing, electrochemicallprocessas and other fields.

- While I have herein described with considerableparticularity one manner of practising the invention, it will be understood I do not desire or intend thereby to limit or confine myself thereto as changes and modifications'ini the rocedure will readily, occur to: those s'killcfd "initli .art' and may be made. ifdesired withoutdeparting;from the spirit and scope off. the y invention; as: defined in the appended claims c Having thus described my, invention, I'L'claim and desire to protect b'y. lletters l atent ofith'e UnitedStates: r

1. The method 1 of producing the I substantially pure mon'ofluorophosphate' offan alkali metal Lot the group consistingofsodium and potassium which comprises subjecting mixed'stoichiorneteric proportions-of Tthe metaphosphate and the fluo ride of the'metal to substantial fusion-and maintaining the mass atabouf'fusion temperature until the reaction "has proceeded substantially.to

completion while excluding"moist' atmosphere from the mass'andconfiningjvapors ir'rth'e con:

taining vessel. V

2. The methodLOf T producing the substantially puremonofl'uorophosphate ot 'an alkali metal 10f the group consisting of"sodium.-andpotassiuin which comprisesmixingtogether in fiheljdividd particles substantially s'toichiometi idpmportions of the metaphosphateZ-and tiie fli'iorid of.- the metal; subjectinguthe mixture to a; temperature of substantial fusion in a closed Tvessel .and main? tainin'gvcit at about that temperature for a" sige nifi'cant' periodofl'tii'ne while confining-vapors within the. vessel and" excludir'iggmoistiair uiereg from, thenncoo'lingjthe reaUtiOnprOdUctSuEStarI- tainingit' at aboutlthat temperature .until the mass has fused substantially, to "a homogeneous liquidwhile confining. vapors within the vessel" and excluding moist" air' therefrom, ,th'en cooling thetreaction product substantialIy-to room tern peraturebefore' openingjthe-rvess'elf' 1 4. The'meth'od'offproducing tli'e substantiallsi' pure vmonofiuorophosphate; oflanlalkali lniet'al i;

the group consisting-g of I. sodium l and potassiumwhich comprises .reactingein ananhydrous substantiall y-closed systematapproximatelythe .fu-

With the fluoride of the metal in accordance with the following equation:

wherein Me represents the metal.

5. The method of producing a monofiuorophosphate which comprises reacting together the fluoride and the metaphosphate of an alkali metal in stoichiometric proportions and substantially at the fusion temperature of the mass.

6. The method of producing substantially pure potassium monofluorophosphate which comprises reacting potassium metaphosphate with potassium fluoride in stoichiometric proportions at a temperature between about 800-900 C. while inhibiting contact of moist air with the reacting mass and escape of vapors therefrom.

7. The method of producing substantially pure sodium monofluorophosphate which comprises reacting sodium metaphosphate with sodium fluoride in stoichiometric proportions at a temperature between about 600-700 C. while inhibiting contact of moist air with the reacting mass and escape of vapors therefrom.

8. The method of producing substantially pure potassium monofluorophosphate which comprises grinding together substantially stoichiometric proportions of potassium metaphosphate and potassium fluoride to reduce them to intimately ingrinding together substantially stoichiometric proportions of sodium metaphosphate and sodium fluoride to reduce them to intimately intermingled finely divided condition, subjecting the mixture to a temperature of about 600-700 C. While confining it within a substantially closed chamber, and cooling the resultant mass in the chamber while excluding moist air therefrom and confining therein vapors produced by the reaction.

CARL O. ANDERSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,220,818 Jelen Nov. 5, 1940 2,408,784 Lange et al. -a Oct. 8, 1946 

